Elastic and stretchable gel polymer electrolyte

ABSTRACT

The present disclosure relates generally to a coated electrode for use in preparation of lithium ion batteries and methods of preparing such. More particularly, the present disclosure relates to a polymer coating composition for coating electrodes of the lithium ion batteries (LIBs). The polymer coating composition comprises a polyurethane gel polymer electrolyte (GPE) formed by a reaction of an isocyanate and a polyol.

FIELD

The presently disclosed and/or claimed inventive process(es),procedure(s), method(s), product(s), result(s), and/or concept(s)(collectively referred to hereinafter as the “present disclosure”)relates generally to a coated electrode for use in lithium ion batteriesand methods of preparing such. More particularly, but not by way oflimitation, the present disclosure relates to a polymer coatingcomposition used for coating electrodes of lithium ion batteries (LIBs).The polymer coating composition comprises a polyurethane gel polymerelectrolyte (GPE) formed by a reaction of an isocyanate and a polyol.Additionally, the present disclosure relates generally to thecompositions and methods of making electrodes, in particular but withoutlimitation, anodes, with the polymer coating composition comprising thepolyurethane GPE.

BACKGROUND

Lithium ion batteries (LIBs) are used in many products including medicaldevices, electric cars, airplanes, and most notably, consumer productssuch as laptop computers, cell phones, and cameras. Due to their highenergy densities, high operating voltages, and low-self discharges,lithium ion batteries have overtaken the secondary battery market andcontinue to find new uses in products and developing industries.

Generally, a lithium ion batteries (LIB) comprises an anode, a cathode,and an electrolyte material such as an organic solvent containing alithium salt. More specifically, the anode and cathode (collectively,“electrodes”) are formed by mixing either an anode active material or acathode active material with a binder and a solvent to form a paste orslurry which is then coated and dried on a current collector (e.g.,aluminum or copper), to form a film on the current collector. The anodesand cathodes are then layered or coiled prior to being housed in apressurized casing containing an electrolyte material, which alltogether forms the LIB.

During charging and discharging of LIBs, significant volume changes inthe electrodes may occur. Such cycling volume changes generate a largestrain on the electrodes resulting in electrode structural damages anddeformations, such as pulverization of the electrode active materials.Volume changes also increase accumulated growth of the solid electrolyteinterface (SEI) layer, which is a passivation layer formed by chemicaland electrochemical reaction of the liquid electrolyte. The formation ofan SEI layer in an LIB is unavoidable, and, when stabilized, essentialto accommodate the large volume change of electrodes. However, when theelectrodes experience large volume changes the SEI layer is destabilizedand overgrowth can occur. The amount of electrode volume change dependslargely upon the type of active material utilized in the electrode.

Silicon has recently come to the forefront as a promising anode activematerial for LIBs. See, for example, B. Lestriez et al., On the BindingMechanism of CMC in Si Negative Electrodes for Li-ion Batteries,Electrochemistry Communications, vol. 9, 2801-2806 (2007), which ishereby incorporated herein by reference in its entirety. Silicon is apromising anode active material because: (a) its high theoreticalspecific capacity of 4200 mAhg⁻¹ for Li_(4.4)Si; (b) its high arealcapacity with the ability to pair with commercial cathodes; (c) its lowelectrochemical potential between 0 and 0.4 V versus Li/Li⁺; and (d) itssmall initial irreversible capacity compared with other metal- oralloy-based anode materials. See, B. Koo et al., A Highly Cross-linkedPolymeric Binder for High-Performance Silicon Negative Electrodes inLithium Ion Batteries, Angew. Chem. Int. Ed. 2012, 51, 8762-8767, herebyincorporated herein by reference in its entirety. It has been found thata specific capacity of about 600 mAhg⁻¹ can be achieved by mixinggraphite with silicon oxide (SiOx) and conductive carbon at a weightratio of about 0.795/0.163/0.042 and, alternatively, a specific capacityof about 450 mAhg⁻¹ can be achieved by mixing graphite with siliconoxide at a weight ratio of about 92 to 5, both of which increase thespecific capacity of the anode material above the 340 mAhg⁻¹ associatedwith graphite independent of any other electrode active material.Silicon has been known, however, to undergo large degrees of expansionand contraction during charging and discharging (i.e., the volumechanges discussed hereinabove), which can degrade a battery's capacityand overall performance.

In each battery cycle, as the electrode active material's siliconparticles undergo expansion and contraction, particles can becomepulverized and parts of the electrode can crack, exposing fresh activesilicon particles on the electrode surface to the liquid electrolyte.Upon such exposure, a new SEI layer forms on the fresh active particlesurface and will bind to lithium ions, causing irreversible loss oflithium ions and poor cycling life. Increased SEI layer formation is theprimary reason for lithium ion loss in each battery cycle.

In order to improve battery life cycle, existing LIB technology teachesthe use of additive compositions in electrode binders to restrict thephysical expansion of the electrode. See, for example, U.S. PatentApplication No. 2006/0235144 to Hwang et al. and U.S. Patent ApplicationNo. 2016/0149216 to Mizuno et al. Electrodes comprising these binderadditives alone do not have the mechanical properties necessary,however, to support the large volume changes that occur with someelectrode active materials. For example, a self-healing polymer has beenused as a binder additive to improve the cycling stability of the anode.See, Wang, Chao, et al. “Self-Healing Energy Lithium-Ion Batteries.”Nature Chemistry, Vol. 1802, 17 Nov. 2013, pp. 1-7.' Doi:10.10238.However, the rate performance of such functional polymer additives isnot significantly improved, and the relative amount of coating polymerused is excessive.

The presently disclosed and/or claimed coating compositions comprising apolyurethane gel polymer electrolyte (GPE), however, improve electrodeadhesion strength and decrease electrode thickness change during thecharge/discharge process of LIBs for long-term cycling stability.Specifically, the GPE coating is elastic and stretchable to accommodatethe volume change of the electrode upon cycling. The GPE coating alsomaintains the electrode integrity for long-term cycling: when theelectrode active material particles get pulverized during cycling, theGPE coating can restrict the pulverized particles and conductive carboninto a small localized space, thereby maintaining the electronic contactbetween cracked particles and conductive carbon. The GPE coatingimproves the cycling stability of LIBs.

SUMMARY

The present disclosure encompasses an electrode coated with a polymercoating composition for use in lithium ion batteries and methods ofpreparing such, the polymer coating composition comprising apolyurethane gel polymer electrolyte. In one non-limiting embodiment,the polyurethane gel polymer electrolyte comprises a polyurethane formedby reacting an isocyanate and a polyol to form a polyurethane solution,which is coated on the electrode.

The present disclosure further encompasses a coated electrode for use ina lithium ion battery comprising an electrode comprising: (1) a filmcomprising: (i) an electrode active material, (ii) a binder composition,and (iii) a conductive agent, and (2) a current collector; and a polymercoating composition comprising a polyurethane gel polymer electrolyte.The polymer coating composition can substantially cover an outer surfaceof the electrode and can be penetrated the electrode. In onenon-limiting embodiment, the polyurethane gel polymer electrolytecomprises a polyurethane formed by a reaction of an aromaticdiisocyanate and a polyether polyol.

Additionally, the present disclosure also encompasses a method of makinga coated electrode for use in preparation of a lithium ion batterycomprising steps of: (1) combining an electrode active material, abinder composition, and a conductive agent to form a slurry; (2)applying the slurry to a current collector to form a coated currentcollector comprising a slurry layer on the current collector; (3) dryingthe slurry layer on the coated current collector to form a film on thecurrent collector, wherein the electrode comprises the film and thecurrent collector; (4) applying a polymer coating composition in solventto the electrode to form a coated electrode having an outer surfacesubstantially covered by the polymer coating composition; and (5)evaporating the solvent from the polymer coating composition to form apolyurethane gel polymer electrolyte coating on the electrode. In onenon-limiting embodiment, the polyurethane gel polymer electrolytecomprises a polyurethane formed by a reaction of an aromaticdiisocyanate and a polyether polyol. In another non-limiting embodiment,the method includes calendaring the electrode of the step (3) prior tothe step (4).

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated in and constitute apart of this specification, illustrate one or more implementationsdescribed herein and, together with the description, explain theseimplementations. The drawings are not intended to be drawn to scale, andcertain features and certain views of the figures may be shownexaggerated, to scale or in schematic in the interest of clarity andconciseness. Not every component may be labeled in every drawing. Likereference numerals in the figures may represent and refer to the same orsimilar element or function. In the drawings:

FIG. 1 is a graphical representation of the capacity retention after 200cycles for the anodes with coatings from the Samples A-1, A-3, B-1, B-2,C-1 and D-3 and without coating, as described below.

FIG. 2 is a graphical representation of the rate capabilities of theanodes with coatings from Samples A-3 and B-3 and without coating asmeasured by their capacity retentions at rates of 0.05 C, 0.2 C, 0.5 C,1 C, and 0.05 C for 4 cycles per rate, as described below.

FIG. 3 is a graphical representation of the impedance of the anodes withcoatings from Samples A-4 and D-3 and without coating, as describedbelow.

FIG. 4 is a graphical representation comparing the electrochemicalperformance of polyurethane-coated anodes from Samples B-2 and C-1 witha polyurethane-urea-coated anode, as described below.

FIG. 5 is another graphical representation comparing the electrochemicalperformance of polyurethane-coated anodes from Samples A-4, B-2 and C-1with a polyurethane-urea-coated anode, as described below.

FIG. 6 is a graphical representation comparing the capacity retention ofthe polyurethane-coated anode from Sample C-1 with the anodes havingpolyurethane-containing binders E-G, as described below.

DETAILED DESCRIPTION

Before explaining at least one embodiment of the present disclosure indetail, it is to be understood that the present disclosure is notlimited in its application to the details of construction and thearrangement of the components or steps or methodologies set forth in thefollowing description or illustrated in the drawings. The presentdisclosure is capable of other embodiments or of being practiced orcarried out in various ways. Also, it is to be understood that thephraseology and terminology employed herein is for the purpose ofdescription and should not be regarded as limiting.

Unless otherwise defined herein, technical terms used in connection withthe present disclosure shall have the meanings that are commonlyunderstood by those of ordinary skill in the art. Further, unlessotherwise required by context, singular terms shall include pluralitiesand plural terms shall include the singular. As used herein, the terms“comprises,” “comprising,” “includes,” “including,” “has,” “having” orany other variation thereof, are intended to cover a non-exclusiveinclusion. For example, a process, method, article, or apparatus thatcomprises a list of elements is not necessarily limited to only thoseelements but may include other elements not expressly listed or inherentto such process, method, article, or apparatus. Further, unlessexpressly stated to the contrary, “or” refers to an inclusive or and notto an exclusive or. For example, a condition A or B is satisfied byanyone of the following: A is true (or present) and B is false (or notpresent), A is false (or not present) and B is true (or present), andboth A and B are true (or present).

All patents, published patent applications, and non-patent publicationsmentioned in the specification are indicative of the level of skill ofthose skilled in the art to which the present disclosure pertains. Allpatents, published patent applications, and non-patent publicationsreferenced in any portion of this application are herein expresslyincorporated by reference in their entirety to the same extent as ifeach individual patent or publication was specifically and individuallyindicated to be incorporated by reference.

All of the articles and/or methods disclosed herein can be made andexecuted without undue experimentation in light of the presentdisclosure. While the articles and methods of the present disclosurehave been described in terms of preferred embodiments, it will beapparent to those of ordinary skill in the art that variations may beapplied to the articles and/or methods and in the steps or in thesequence of steps of the method described herein without departing fromthe concept, spirit and scope of the present disclosure. All suchsimilar substitutes and modifications apparent to those skilled in theart are deemed to be within the spirit, scope and concept of thedisclosure.

As utilized in accordance with the present disclosure, the followingterms, unless otherwise indicated, shall be understood to have thefollowing meanings.

The use of the word “a” or “an” when used in conjunction with the term“comprising” may mean “one,” but it is also consistent with the meaningof “one or more,” “at least one,” and “one or more than one.” The use ofthe term “or” is used to mean “and/or” unless explicitly indicated torefer to alternatives only if the alternatives are mutually exclusive,although the disclosure supports a definition that refers to onlyalternatives and “and/or.” Throughout this application, the term “about”is used to indicate that a value includes the inherent variation oferror for the quantifying device, the method being employed to determinethe value, or the variation that exists among the study subjects. Forexample, but not by way of limitation, when the term “about” isutilized, the designated value may vary by plus or minus twelve percent,or eleven percent, or ten percent, or nine percent, or eight percent, orseven percent, or six percent, or five percent, or four percent, orthree percent, or two percent, or one percent. The use of the term “atleast one” will be understood to include one as well as any quantitymore than one, including but not limited to, 1, 2, 3, 4, 5, 10, 15, 20,30, 40, 50, 100, etc. The term “at least one” may extend up to 100 or1000 or more depending on the term to which it is attached. In addition,the quantities of 100/1000 are not to be considered limiting as lower orhigher limits may also produce satisfactory results. In addition, theuse of the term “at least one of X, Y, and Z” will be understood toinclude X alone, Y alone, and Z alone, as well as any combination of X,Y, and Z. The use of ordinal number terminology (i.e., “first”,“second”, “third”, “fourth”, etc.) is solely for the purpose ofdifferentiating between two or more items and, unless explicitly statedotherwise, is not meant to imply any sequence or order or importance toone item over another or any order of addition.

As used herein, the words “comprising” (and any form of comprising, suchas “comprise” and “comprises”), “having” (and any form of having, suchas “have” and “has”), “including” (and any form of including, such as“includes” and “include”) or “containing” (and any form of containing,such as “contains” and “contain”) are inclusive or open-ended and do notexclude additional, unrecited elements or method steps. The term “orcombinations thereof” as used herein refers to all permutations andcombinations of the listed items preceding the term. For example, “A, B,C, or combinations thereof” is intended to include at least one of: A,B, C, AB, AC, BC, or ABC and, if order is important in a particularcontext, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing withthis example, expressly included are combinations that contain repeatsof one or more item or term, such as BB, AAA, AAB, BBC, AAABCCCC,CBBAAA, CABABB, and so forth. The skilled artisan will understand thattypically there is no limit on the number of items or terms in anycombination, unless otherwise apparent from the context.

As used herein, the term “substantially” means that the subsequentlydescribed event or circumstance completely occurs or that thesubsequently described event or circumstance occurs to a great extent ordegree. For example, the term “substantially covers” means that apolymer coating composition covers at least about 70%, or at least about75%, or at least about 80%, or at least about 85%, or at least about90%, or at least 95% of the surface area of an outer surface of anelectrode. The term “substantially free” as used herein means less than5 wt %, or 3 wt %, or 2 wt %, or 1 wt %, or 0.5 wt %, or 0.1 wt %.

A coated electrode of the present disclosure generally comprises,consists of, or consists essentially of an electrode comprising (1) afilm comprising: (i) an electrode active material, (ii) a bindercomposition, and (iii) a conductive agent, and (2) a current collector;and a polymer coating composition comprising a polyurethane gel polymerelectrolyte, wherein the polymer coating composition substantiallycovers an outer surface of the electrode. The polyurethane gel polymerelectrolyte comprises a polyurethane formed by a reaction of anisocyanate and a polyol. In one non-limiting embodiment, the reaction issubstantially free of polyamine chain extenders. The polymer coatingcomposition can generally be used in the manufacture of a coatedelectrode for use in the production of a lithium ion battery (LIB).

In one non-limiting embodiment, the isocyanate is a diisocyanate havingat least two isocyanate groups. The diisocyanate may include aromaticdiisocyanates, aliphatic diisocyanates, or combinations thereof. In someembodiments, the diisocyanate includes one or more aromaticdiisocyanates. More specifically, the diisocyanate may be selected fromthe group consisting of aromatic diisocyanates such as4,4′-methylenebis(phenyl isocyanate) (MDI), m-xylene diisocyanate (XDI),phenylene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, and toluenediisocyanate (TDI); and aliphatic diisocyanates such as isophoronediisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CNDI),decane-1,10-diisocyanate, lysine diisocyanate (LDI), 1,4-butanediisocyanate (BDI), 3,3′-dimethyl-4,4′-biphenylene diisocyanate (TODI),1,5-naphthalene diisocyanate (NDI), anddicyclohexylmethane-4,4′-diisocyanate (H12MDI). Mixtures of two or morediisocyanates may be used. In particular, but without limitation, thediisocyanate may be MDI.

The polyol may be a polyether polyol. Suitable polyether polyols includepoly(ethylene glycol) derived from ethylene oxide reacted with ethyleneglycol, poly(propylene glycol) derived from propylene oxide reacted withpropylene glycol, poly(tetramethylene ether glycol) derived from waterreacted with tetrahydrofuran which can also be described as polymerizedtetrahydrofuran, and which is commonly referred to aspoly(tetrahydrofuran) (PTHF). Copolyethers can also be utilized in thedescribed compositions. More specifically, the polyether polyol can beselected from the group consisting of polyethylene glycol, polypropyleneglycol, copolymers of ethylene glycol and propylene glycol such aspoly(oxypropylene)-poly(oxyethylene glycol), and PTHF. In particular,but without limitation, the polyol may be PTHF. The polyol may have anumber average molecular weight (Me) in a range of from about 1,000 toabout 3,500 Daltons, or from about 1,000 to about 2,500 Daltons, or fromabout 1,000 to about 1,600 Daltons.

The polyurethane gel polymer electrolyte may comprise a polyurethaneformed by a reaction of an isocyanate with a polyol. The molar ratio ofthe polyol to the isocyanate for the reaction may be in a range of fromabout 1.0:1.2 to about 1.0:2.0, or from about 1.0:1.5 to about 1.0:1.8.In one non-limiting embodiment, the isocyanate is MDI, and the polyol isPTHF. The molar ratio of PTHF to MDI is about 1.0:1.5.

In one non-limiting embodiment, a quenching agent can be added to thereaction comprising an aromatic diisocyanate and a polyether polyol. Thequenching agent may be a C₁-C₄ alcohol. In particular, the quenchingagent may be selected from the group consisting of methanol, ethanol,isopropanol, and butanol.

The polyurethane gel polymer electrolyte can be solution-coated on theelectrode. By solution-coated, it is meant that a solution comprisingthe polyurethane and a solvent is applied to the electrode and then thesolvent is evaporated, which leaves the polyurethane gel polymerelectrolyte coated on the electrode. In one non-limiting embodiment, thepolyurethane is present in the solution in a range of from about 1% toabout 25% by weight, or from about 1% to about 15% by weight, or fromabout 5% to about 15% by weight, or from about 5% to about 10% byweight, or from about 10% to about 15% by weight. The solvent can beselected from the group consisting of N,N-dimethylacetamide (DMAc),N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), dimethyl sulfoxide(DMSO), tetramethylsilane (TMS), and dimethylformamide (DMF).

By solution-coating the polyurethane gel polymer electrolyte onto theelectrode, the gel polymer electrolyte maintains a sufficient lowviscosity, thereby allowing the coating to penetrate the electrode voidspace and uniformly distribute on and within the electrode, therebycoating the electrode's surface. The solution-coated gel polymerelectrolyte forms a stretchy and transparent membrane on the surface ofthe electrode and within the electrode void space. Additionally, thesolution-coated gel polymer electrolyte contains micropores for enhancedion storage and mobility. Solution-coating does not include applicationby temperature, such as, melt coating, bar coating, heat lamination, hotmelt extrusion, and co-extrusion. Solution-coating allows for improvedion permeability over temperature application methods.

The coated electrode includes an electrode comprising, consisting of, orconsisting essentially of 1) a film comprising (i) an electrode activematerial, (ii) a binder composition, and (iii) a conductive agent; and(2) a current collector. In one embodiment, the electrode activematerial is present in the film in a range of from about 65 to about 89wt %, or from about 70 to about 90.5 wt %, or from about 75 to about 93wt %; the conductive carbon is present in a range of from about 1 toabout 10 wt %, or from about 1 to about 8 wt %, or form about 1 to about5 wt %; and the binder composition is present in the film in a range offrom about 1 to about 34 wt %, or from about 1.5 to about 29 wt %, orfrom about 2 to about 24 wt %.

The coated electrode has a thickness in a range of from about 15 toabout 70 μm, or from about 15 about 50 μm, or from about 15 μm to about30 μm. The current collector can comprise any material that acts as anelectrical conductor for either the anode or cathode active materials.The current collector can be selected from the group consisting ofaluminum, carbon, copper, stainless steel, nickel, zinc, silver, andcombinations thereof. In one non-limiting embodiment, the currentcollector for the anode comprises copper foil. In another non-limitingembodiment, the current collector for the cathode comprises aluminumfoil.

The binder composition of the present disclosure generally comprises anionizable water soluble polymer. The binder composition may furtherinclude a redispersible powder which can comprise, consist of, orconsist essentially of a protective colloid (also referred to as a“redispersing aid”), an anticaking agent, and a latex polymer. Theionizable water soluble polymer can be any material selected from thegroup consisting of a hydrophilically modified cellulose material,polyacrylic acid, a polyacrylic acid copolymer, polyacrylamide, anacrylamide copolymer, alginate, xanthan gum, polyvinyl alcohol,anionically modified polysaccharide, lithiated alginate, lithiatedxanthan gum, lithiated polyacrylic acid, lithiated polyvinyl alcohol, alithiated anionically modified polysaccharide, and combinations thereof.The anionically modified polysaccharide can be selected from the groupconsisting of carboxyalkyl cellulose, carboxyalkyl hydroxyalkylcellulose, carboxyalkyl guaran, carboxyalkyl hydroxyalkyl guaran, andcombinations thereof. The lithiated anionically modified polysaccharidecan be selected from the group consisting of lithiated carboxyalkylcellulose, lithiated carboxyalkyl hydroxyalkyl cellulose, lithiatedcarboxyalkyl guaran, lithiated carboxyalkyl hydroxyalkyl guaran, andcombinations thereof. For example, but without limitation, the SoterasMSi binder available from Ashland, Inc. (Wilmington, Del.) can be usedin the present disclosure. In one non-limiting embodiment, the bindercomposition is substantially free of polyurethane polymer. In anothernon-limiting embodiment, the binder composition is substantially free oflatex.

The electrode active material can be an anode active material. The anodeactive material can be any material comprising, consisting of, orconsisting essentially of (1) at least one of an artificial graphite, anatural graphite, surface modified graphite, coke, hard carbon, softcarbon, carbon fiber, conductive carbon, and combinations thereof, (2)silicon-based alloys, (3) complex compounds comprising, consisting of,or consisting essentially of: i) at least one of artificial graphite,natural graphite, surface modified graphite, coke, hard carbon, softcarbon, carbon fiber, conductive carbon and combinations thereof, andii) a metal selected from the group consisting of Al, Ag, Bi, In, Ge,Mg, Pb, Si, Sn, Ti, and combinations thereof, (4) a lithium complexmetal oxide, (5) lithium-containing nitrides, (6) silicon-graphene, (7)a silicon-carbon nanotube, (8) silicon oxide, and (9) combinationsthereof.

The anode active material, in one non-limiting embodiment, can beselected from the group consisting of artificial graphite, naturalgraphite, surface modified graphite, coke, hard carbon, soft carbon,carbon fiber, conductive carbon, and combinations thereof. In anothernon-limiting embodiment, the anode active material comprises a complexcompound comprising, consisting of, or consisting essentially of (i) atleast one of artificial graphite, natural graphite, surface modifiedgraphite, coke, hard carbon, soft carbon, carbon fiber, conductivecarbon, and combinations thereof, and (ii) silicon and/or silicon oxide.The anode active material, in yet another non-limiting embodiment, cancomprise, consist of, or consist essentially of lithium titanate oxide(LTO).

In one non-limiting embodiment, the anode active material can be siliconoxide. In another non-limiting embodiment, the anode active material canbe a mixture of graphite and silicon oxide, wherein the silicon oxidecan, for example but without limitation, be represented by the formulaSiOx, wherein X can be either one or less than 2 and further wherein theweight ratio of the graphite to the silicon oxide may be at least 50:50,or in a range of from about 99:1 to about 1:99, or from about 80:20 toabout 95:5, or from about 90:10 to about 95:5. In one non-limitingembodiment, the above-described anode active material comprisinggraphite and silicon oxide can also comprise conductive carbon in arange from about 0.1 to about 10 wt %, or from about 1 to about 8 wt %,or from about 2 to about 5 wt %.

In another non-limiting embodiment, the anode active material maycomprise a silicon-graphene composition and/or a combination of asilicon-graphene composition and graphene. See, for example but withoutlimitation, the XG-SIG™ silicon-graphene nano-composite materialavailable from XG Sciences, Inc. (Lansing, Mich.). In yet anothernon-limiting embodiment, the electrode active material may comprise asilicon alloy, for example but without limitation, STN, and/or a mixtureof a silicon alloy and graphite. More specifically, the electrode activematerial may comprise silicon alloy and graphite mixture, wherein thesilicon alloy is present in a range of from about 30 to 50 wt %, or fromabout 35 to about 45 wt %, or from about 37.5 to about 42.5 wt %, andwherein the graphite is present in a range from about 50 to about 70 wt%, or from about 55 to about 65 wt % or from about 57.5 to about 62.5 wt%.

In one non-limiting embodiment, the above-described anode activematerial may comprise a combination of a silicon-graphene compositionand graphite, further comprising conductive carbon. More specifically,the anode active material may comprise silicon-graphene and graphiteand/or conductive carbon, wherein the silicon-graphene is present in arange of from about 20 to 95 wt %, or from about 70 to 95 wt %, or fromabout 75 to 95 wt %, or from about 80 to about 95 wt %, and wherein thegraphite is present in a range of from about 5 to about 30 wt %, or fromabout 10 to about 25 wt %, or from about 10 to about 20 wt %, andwherein the conductive carbon is present in a range of from about 1 toabout 10 wt %, or from about 1 to about 8 wt %, or form about 1 to about5 wt %.

The electrode active material can be a cathode active material. Thecathode active material can be any material comprising, consisting of,or consisting essentially of lithium-containing transition metal oxides.The cathode active material, in one non-limiting embodiment, can beselected from the group consisting of lithium iron phosphate (LiFePO₄),lithium cobalt oxide (LiCoO₂), lithium nickel oxide (LiNiO₂), lithiumnickel cobalt aluminum oxide (LiNiCoAlO₂), lithium nickel manganesecobalt oxide (LiNiMnCoO₂), lithium manganese oxide (LiMn₂O₄), andcombinations thereof.

The conductive agent can be conductive carbon, carbon nanotubes, carbonblack, carbon fiber, graphite, graphene, and combinations thereof.

The current collector can be any material that acts as an electricalconductor for either the anode active material or the cathode activematerial. For example, but without limitation, the current collector canbe selected from the group of materials comprising, consisting of, orconsisting essentially of aluminum, carbon, copper, stainless steel,nickel, zinc, silver, and combinations thereof. In one non-limitingembodiment, the current collector for the anode is a copper foil. Inanother non-limiting embodiment, the current collector for the cathodeis an aluminum foil.

It has been unexpectedly discovered that the coated electrode of thepresent disclosure greatly improves battery cycle life. Morespecifically, the polyurethane gel polymer electrolyte coating increaseselectrode adhesion strength and decreases electrode thickness changeduring the charge/discharge cycling process of LIBs thereby increasingcycling stability for long-term use. The GPE coating also maintains theelectrode integrity for long-term cycling: without being bound bytheory, when the electrode active material particles are pulverizedduring cycling, the GPE coating restricts the pulverized particles andconductive carbon into a small localized space, thus maintaining theelectronic contact between cracked particles and conductive carbon. Asshown in the Examples, an electrode coated with the polyurethane gelpolymer electrolyte of the present disclosure greatly improves batterycycling life as compared to known electrodes which include apolyurethane gel polymer within the electrolyte binder.

The present disclosure additionally encompasses a method of making acoated electrode for a lithium ion battery comprising steps of: (1)combining an electrode active material, a binder composition, and aconductive agent to form a slurry; (2) applying the slurry to a currentcollector to form a coated current collector comprising a slurry layeron the current collector; (3) drying the slurry layer on the coatedcurrent collector to form a film on the current collector, wherein theelectrode comprises the film and the current collector; (4) applying apolymer coating composition in solvent to the electrode to form a coatedelectrode having an outer surface substantially covered by the polymercoating composition; and (5) evaporating the solvent from thepolyurethane coating composition to form a polyurethane gel polymerelectrolyte coating on the electrode. In one embodiment, the methodincludes calendaring the electrode of the step (3) prior to the step(4).

In one non-limiting embodiment, the electrode active material is presentin the film in a range of from about 65 to about 89 wt %, or from about70 to about 90.5 wt %, or from about 75 to about 93 wt %; the conductivecarbon is present in a range of from about 1 to about 10 wt %, or fromabout 1 to about 8 wt %, or form about 1 to about 5 wt %; and the bindercomposition is present in the film in a range of from about 1 to about34 wt %, or from about 1.5 to about 29 wt %, or from about 2 to about 24wt %. In one embodiment, a mass ratio of the electrode active materialto the conductive agent to the binder composition is about 8:1:1.

The polyurethane coating composition has a polyurethane mass loading ina range of from about 0.1 mg/cm² to about 0.9, or from 0.2 mg/cm² toabout 0.7 mg/cm², or from 0.2 mg/cm² to about 0.5 mg/cm². In oneembodiment, the mass loading is about 0.3 mg/cm².

In one non-limiting embodiment, the polyurethane gel polymer electrolyteis solution-coated on the electrode. By solution-coated, it is meantthat a solution comprising polyurethane and solvent is applied to theelectrode to form a coated electrode, and then the solvent isevaporated, which leaves the polyurethane gel polymer electrolyte coatedon the electrode. A dilute solution of polyurethane in solvent can beapplied to the electrode. In one non-limiting embodiment, thepolyurethane is present in the solution in a range of from about 1% toabout 25%, or from about 5% to about 15%, or from about 5% to about 10%,or from about 10% to about 15% by weight. The solvent can be selectedfrom the group consisting of N,N-dimethylacetamide (DMAc),N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), dimethyl sulfoxide(DMSO), tetramethylsilane (TMS) and dimethylformamide (DMF).

In an additional embodiment the above-described electrodes have animpedance less than about 300 ohms, or less than about 250 ohms, or lessthan about 200 ohms, wherein the film thickness is in a range of fromabout 15 to about 70 μm, or from about 15 to about 50 μm, or from about15 to 30 μm.

EXAMPLES

Polyurethane Preparation and Characterization

42.92 g poly(tetrahydrofuran) (“PTHF”) was dried at 80° C. under vacuumof 29 in. Hg for 4-6 hours. The PTHF was cooled to 20-24° C. in adessicator. Stock solution of N,N,N′,N″,N″-Pentamethyldiethylenetriamine(PMDTA) in N,N-Dimethylacetamide (DMAc) was prepared by: (1) adding 0.44g PMDTA to 8.36 g DMAc in a dried glass vial, (2) gently shaking thesolution, and (3) storing the solution under nitrogen.

To a dry glass resin kettle equipped with a reflux condenser, amechanical agitator, a thermocouple, and a nitrogen inlet was added dryPTHF under a steady stream of nitrogen. The reactor was heated to 80° C.172.96 g DMAc, 4.78 g MDI for Polymers A-C and 5.72 g MDI for Polymer D,and 0.88 g PMDTA/DMAc stock solution were added into the reactor. Thecontents of the reactor were heated at 80° C. and mixed under a steadystream of nitrogen for a certain time listed as TIME1 in Table 1. Thecontents of the reactor were cooled to a temperature around 55-60° C. toobtain solutions of Polymers A-D. Different samples were prepared fromthe polymer solutions. Approximately 50% of the contents of the reactorwere removed to provide unquenched polymer solutions. To the remainingsolution in the reactor was added MeOH (10 g) and dibutyltin dilaurate(DBTD) (1-2 drops). The resultant polymer solution was mixed at atemperature between 55-60° C. for a certain time as TIME2 listed inTable 1.

A film was prepared from the above polymer solution as follows. Thepolymer solution was poured onto a glass petri dish and heated at 120°C. under vacuum of 29 in. Hg for 4-6 hours to remove DMAc. Once cooledto 20-24 ° C., the film was removed from the petri dish.

Size Exclusion Chromatography (SEC) was used for measuring polyurethanemolecular weight distributions. A Waters HPLC System and Empower™Chromatography Data System, commercially available from the WatersCorporation (Milford, Mass.) were used to measure the molecular weights.As used herein with respect to polymers, the terms molecular weight andmolecular weight averages are defined in ASTM D3016-97 as measured bySEC. The relative molecular weight averages from the SEC were calculatedversus polystyrene standards with narrow molecular weight distribution.Table 1 lists the reaction time and samples prepared from each PolymerA-D as well as SEC molecular weights for each sample.

TABLE 1 TIME1 Sample TIME2 SEC Polymer min Sample Description min Mn MwMz A 60 A-1 Film prepared 25,600 67,900 112,000 from unquenched polymersolution A-2 Film from 30 26,000 69,800 118,000 quenched polymersolution with MeOH/DBTD A-3 Unquenched 30,500 94,600 161,000 polymersolution A-4 Quenched polymer 19,900 61,600 99,900 solution withMeOH/DBTD B 120 B-1 Film prepared 37,000 105,000 176,000 from unquenchedpolymer solution B-2 Film prepared 40 34,500 104,000 181,000 fromquenched polymer solution with MeOH/DBTD C 180 C-1 Film prepared 39,100133,000 239,000 from unquenched polymer solution C-2 Film prepared 5850,200 171,000 318,000 from quenched polymer solution with MeOH/DBTD D60 D-1 Film prepared 33,200 202,000 587,000 from unquenched polymersolution D-2 Film prepared 55 25,300 139,000 419,000 from quenchedpolymer solution with MeOH/DBTD D-3 Unquenched 57,800 397,000 1,190,000polymer solution

Anode Preparation

An anode was prepared for coating and testing. 12.2 g SiO_(x),commercially available from Osaka Titanium Technologies Co., Ltd.(Amagasaki, Hyogo Prefecture, Japan) was used as an anode activematerial. 1.53 g conductive carbon, C-NERGY™ Super C65, commerciallyavailable from Timcal Graphite & Carbon (Bodio, Switzerland) was used asa conductive agent. 1.52 g Soteras™ MSi, commercially available fromAshland LLC. (Wilmington, Del., USA) was used as a binder composition.

A slurry was prepared by (1) dissolving the Soteras™ MSi in water toform a 2 wt % aqueous binder solution; (2) adding the conductive carbonpowder to the aqueous binder solution; (2) adding water and mixing thecompositions with a Thinky® mixer (available from Thinky Corporation,Tokyo, Japan) to disperse the conductive carbon powder in the solution.The total water added was 89.94 g. The mass ratio of the anode activematerial to the conductive carbon to the binder composition in theslurry was about 8:1:1.

The anode was prepared by: (1) coating the slurry on a copper foilcurrent collector to form the anode, (2) heating the anode at 60° C. ina conventional oven for 30 minutes, (3) increasing the temperature to80° C. and heating for 30 minutes, (4) increasing the temperature to100° C. and heating for 30 minutes, (5) increasing the temperature to120° C. and heating for 120 minutes, and (6) thereafter cooling theanode.

The coated anode was prepared by coating the polyurethane solution inDMAc on the anode prepared as above. For the polyurethane film listed inTable 1, the film was dissolved in DMAc to form a polyurethane solution.The polyurethane concentration was adjusted to about 6-8 wt % in thepolyurethane solution for coating the anode. The polyurethane solutionwas then coated on the anode at ambient conditions.

Electrochemical Test

Preparation of Half Coin Cells

Half coin cells having a 20 mm diameter and a 3.2 mm height (CR-2032half coin cells) were made using the anodes prepared above incombination with lithium metal disc cathodes, a polyolefin separator,and an electrolyte of 1 mol/L LiPF₆ in a mixture of ethylene carbonate,diethyl carbonate, and dimethyl carbonate (EC: DEC:DMC, 1:1:1 by weight)with 10 w % fluoroethylene carbonate (FEC). Lithium hexafluorophosphate(LiPF₆) was used as the lithium salt. The half coin cells were subjectedto cyclic and rate capability tests as various rates, as well as a testto determine impedance of the half coin cells.

Discharge Capacity Test

In a formation cycle, the cell was cycled between 0.01 V and 1.5 V usinga current rate of 0.05 C, which helped to form stable SEI. The dischargecapacities for the half coin cells prepared above were evaluated at20-24° C., using a current rate of 0.3 C wherein the coated anodes had afilm thickness of from about 15 μm to about 70 μm. The anodes wereevaluated in the voltage range from 0.01 V to 1.5 V versus Li/Li⁺, witha 10 minutes rest time between charging and discharging. A constantvoltage (CV) mode and a constant current (CC) mode were used in the caseof the charging state, i.e. Li insertion into the SiO_(x), and thedischarge state, i.e., Li extraction from SiO_(x), respectively. Theresults are shown in FIG. 1 which was obtained from the 200 cycles. Itcan be seen that polyurethane GPE coating have higher specific capacityand better retention than anodes prepared without a polyurethane GPEcoating.

Rate Capability Test—Lifecycle Characteristics

The rate capabilities of the half coin cells prepared from Samples A-3and B-3 were evaluated at 20-24° C., in a voltage window of 0.01 V to1.5 V, for a range by charging and discharging the cells using CC/CCmode at a rate of 0.05 C, 0.2 C, 0.5 C, 1 C and 0.05 C for 4 cycles perrate, wherein the coated anodes had a thickness of from 15 μm and 70 μm.The areal loading for the anode was 1.8 mg SiO_(x)/cm². The results areshown in FIG. 2 and indicate that anodes prepared with a polyurethaneGPE coating have higher specific capacity than anodes prepared without apolyurethane GPE coating.

Impedance

Impedance of the above-described 2032 half coin cells prepared fromSamples A-4 and D-3 were tested for impedance. The battery impedancedata was measured using a Solartron® 1260 from Solartron Analytical(Leicester, UK). The results are shown in FIG. 3.

Comparison of Polyurethane with Polyurethane-Urea (PUU)

Poly (tetrahydrofuran) (PTHF, Mw=2900), methylene diphenyl diisocyanate(MDI), ethylene diamine (EDA), dimethylacetamide (DMAc, anhydrous), andpentamethyldiethylenetriamine were purchased from Sigma-Aldrich anddirectly used without purification.

The PTHF was dried under vacuum at 110° C. overnight to remove theresidue water. The PUU was synthesized via two steps.

In the first step, 1 mmol of PTHF was firstly dissolved in 13.6 g DMAcat 80° C. in a 50 mL three-neck flask. 2 mmol MDI was then added anddissolved to form solution in the flask. Pentamethyldiethylenetriamine(0.1 w %, with respect to the reactant) in DMAc was added to thesolution as a catalyst to form a mixture. The mixture was stirred at 80°C. for 4 h under dry nitrogen to get PTHF-2MDI intermediate solutionwith two isocyanate end groups. The solution was cooled down to about20-25° C. before the addition of EDA.

In the second step, 1.05 mmol of EDA (ethylene diamine) in DMAc wasadded to the intermediate solution. (As EDA evaporated very fast, EDAwas dispersed in DMAc to get 20 w % solution and the amounts of aminogroups was 5% excessive than isocyanate groups.) The mixture was stirredat 80° C. for 4 h under dry nitrogen. After pouring the mixture into aTeflon mode and evaporating the solvent, a transparent and stretchablePUU film was obtained.

The PUU film was then dissolved in DMAc to form a polyurethane-ureasolution. The PUU concentration was adjusted to about 6-8 wt % in thePUU solution for coating the anode. The PUU solution was then coated onthe anode at ambient conditions.

The comparison of the electrochemical performance of polyurethaneGPE-coated anodes with a polyurethane-urea-coated anode is shown inTable 2, and FIGS. 4 and 5. The results presented in FIGS. 4 and 5suggest that anodes prepared with a polyurethane GPE coating have bettercapacity retention than anodes prepared with a polyurethane-urea GPEcoating.

TABLE 2 Capacity Capacity Capacity retention retention retention @50cycle @100 cycle @200 cycle Sample (%) (%) (%) Blank 83 46 24 PUU 83 5536 A-4 92 — — B-2 96 83 65 C-1 91 80 64

Polyurethane Used as a Binder Composition

An anode was prepared using polyurethane as a binder composition ratherthan as a coating. 3.80 g Ashland™ 981 Carbomer (a cross-linked polymerof acrylic acid, commercially available from Ashland LLC, Wilmington,Del.) was dissolved in 120.01 grams of NMP to form a binder solution.50.00 g of the binder solution and 2.50 g of C-NERGY™ Super C65 wereadded and mixed into a 200-ml Thinky Mixer cup. 20.00 g of NMP and 20,00g of SiO_(x) were added into the cup to form a slurry. Sample C-1 filmwas dissolved in DMAc to form a 20 wt % polyurethane solution. 5.00 g ofthe polyurethane solution along with 5.00 g of NMP were added into thecup. The formed slurry was transferred to a 4-ounce glass jar with a capand stored overnight. The mass ratio of anode active material toconductive carbon to Carbomer and the polyurethane was about 80:10:6:4.Three samples E, F and G were prepared based on the above procedure.

Table 3 presents comparison data of the analytical, impedance, and ratecapabilities of the polyurethane-coated anode from Sample C-1 with theanodes of samples E, F, and G used as binders. FIG. 6 graphicallypresents the capacity retention data of the samples listed in Table 3and obtained for the entire 100 cycles.

TABLE 3 Electrode Impedance Density Loading Fresh Cell Sample (g/cm³)(mg/cm²) (ohms) ICE/2^(nd) CE % C-1 1.04 1.70 191.3 73.5/96.1 E 0.912.15 114.6 69.8/86.5 F 0.91 2.20 143.7 70.5/82.8 G 0.95 2.26 158.267.7/75.8

FIG. 6 demonstrates that the cyclic performance of thepolyurethane-coated electrode without polyurethane in the binder isgreatly improved as compared to the cyclic performance of the electrodecontaining a polyurethane binder and no polyurethane coating. Thecapacity for the polyurethane binder samples declined very quickly ascompared to the polyurethane coating sample.

Thus, it should be apparent that there has been provided in accordancewith the present invention an improved coating composition for use on anelectrode, that fully satisfies the objectives and advantages set forthabove. Although the invention has been described in conjunction withspecific embodiments thereof, it is evident that many alternatives,modifications, and variations will be apparent to those skilled in theart. Accordingly, it is intended to embrace all such alternatives,modifications, and variations that fall within the spirit and broadscope of the appended claims.

1. A coated electrode for use in preparation of a lithium ion battery,comprising: an electrode comprising: (1) a film comprising) an electrodeactive material, (ii) a binder composition, and (iii) a conductiveagent; and (2) a current collector; and a polymer coating compositioncomprising a. polyurethane gel polymer electrolyte, wherein the polymercoating composition substantially covers an outer surface of theelectrode.
 2. The electrode of claim 1, wherein the polyurethane gelpolymer electrolyte comprises a polyurethane formed by a reaction of (i)isocyanate and (ii) a polyol.
 3. The electrode of claim 2, wherein theisocyanate is an aromatic diisocyanate.
 4. The electrode of claim 3,wherein the isocyanate is 4,4′-methylenebis(phenyl isocyanate)
 5. Theelectrode of claim 2, wherein the polyol is a polyether polyol.
 6. Theelectrode of claim 5, wherein the polyol poly(tetrahydrofuran),
 7. Theelectrode of claim 2, wherein a molar ratio of the polyol to theisocyanate is in a range of from about 1.0:1.2 to about 1.0:2.0.
 8. Theelectrode of claim 7, wherein the molar ratio of the polyol to theisocyanate is about 1.0:1.5.
 9. The electrode of claim 2, wherein thepolyol has a number average molecular weight in arrange of from about1,000 to about 3,500 Daltons.
 10. The electrode of claim 9, wherein thepolyol has a number average molecular weight of about 1,570 Daltons. 11.The electrode of claim 2, wherein the reaction is substantially free ofethylene diamine.
 12. The electrode of claim 2, wherein the reaction isquenched by a quenching agent.
 13. The electrode of claim 12, whereinthe quenching agent is selected from the group consisting of methanol,ethanol, isopropanol and butanol,
 14. The electrode of claim 1, whereinthe polymer coating composition is solution-coated on the electrode. 15.The electrode of claim 1, wherein the electrode active material is ananode active material.
 16. The electrode of claim 15, wherein the anodeactive material is selected from the group consisting of (A) acarbonaceous material, (B) a silicon- based alloy, (C) a complexcompound comprising a carbonaceous material and a metal selected fromthe group consisting of Al, Ag, Bi, Ge, Mg, Pb, Si, Sn, Ti, andcombinations thereof, (D) a lithium complex metal oxide, (E) alithium-containing nitride, and (F) combinations of componentscomprising items (A)-(E).
 17. The electrode composition of claim 16,wherein the anode active material comprises graphite and silicon oxide,wherein a weight ratio of the graphite to the silicon oxide is in arange of from about 99:1 to about 1:99.
 18. The electrode of claim 1,wherein the binder composition is substantially free of polyurethane.19. The electrode of claim 1, wherein the conductive agent is conductivecarbon.
 20. The electrode of claim 1, wherein the current collector isselected from the group consisting of aluminum, carbon, copper,stainless steel, nickel, zinc, silver, and combinations thereof.
 21. Amethod of making a coated electrode for use in preparation of a lithiumion battery comprising: combining (1) an electrode active material, (2)a binder composition, and (3) a conductive agent to form a slurry;applying the slurry to a current collector to form a coated currentcollector comprising a slurry layer on the current collector; drying theslurry layer on the coated current collector to form a film on thecurrent collector, wherein the electrode comprises the film and thecurrent collector; applying a polymer coating composition in solvent tothe electrode to form a coated electrode having. an outer surfacesubstantially covered by the polymer coating composition; andevaporating the solvent from the polymer coating composition to form apolyurethane gel polymer electrolyte coating on the electrode.
 22. Themethod of claim 21, wherein a mass ratio of the electrode activematerial to the conductive agent to the binder composition is about8:1:1.
 23. The method of claim 21, wherein the polymer coatingcomposition has a mass loading in a range of from about 0.1 mg/cm² toabout 0.9 mg/cm².
 24. The method of claim 21, wherein the polyurethanegel polymer electrolyte comprises a polyurethane formed by a reactioncomprising (i) an isocyanate and (ii) a polyol.
 25. The method of claim24, wherein the polyurethane is present in the polymer coatingcomposition in a range of from about 1% to about 25% by weight.
 26. Themethod of claim 24, wherein the isocyanate is an aromatic diisocyanate.27. The method of claim 26, wherein the aromatic isocyanate is4,4′-methylenebis(phenyl isocyanate).
 28. The method of claim 24,wherein the polyol is a polyether polyol.
 29. The method, of claim 28,wherein the polyether polyol is poly(tetrahydrofuran).
 30. The method ofclaim 24, wherein a molar ratio of the polyol to the isocyanate is in arange of from about 1.0:1.2 to about 1.0:2.0.
 31. The method of claim30, wherein the molar ratio of the polyol to the isocyanate is about1.0:1.5.
 32. The method of claim 24, wherein the polyol has a numberaverage molecular weight in a range of from about 1,000 to about 3,500Daltons.
 33. The method of claim 32, wherein the polyol has a numberaverage molecular weight of about 1,570 Daltons.
 34. The method of claim24, wherein the reaction is substantially free of ethylene diamine. 35.The method of claim 21, wherein the polymer coating composition issolution-coated an the electrode.
 36. The method of claim 21, whereinthe electrode active material is an anode active material.
 37. Themethod of claim 36, wherein the anode active material is selected fromthe group consisting of (A) a carbonaceous material, (B) a silicon-basedalloy, (C) a complex compound comprising a carbonaceous material and ametal selected from the group consisting of Al, Ag, Bi, Ge, Mg, Pb, Si,Sn, Ti, and combinations thereof, (D) a lithium complex metal oxide, (E)a lithium-containing nitride, and (F) combinations of componentscomprising items (A)-(E).
 38. The method of claim 37, wherein the anodeactive material comprises graphite and silicon oxide, wherein a eightratio of the graphite to the silicon oxide is in a range of from about99;1 to about 1:99.
 39. The method of claim 21, wherein the bindercomposition is substantially free of polyurethane.
 40. The method ofclaim 21, wherein the conductive agent is selected from the groupconsisting of conductive carbon, carbon nanotubes, carbon black, carbonfiber, graphite, graphene, and combinations thereof.
 41. The method ofclaim 21, wherein the current collector is selected from the groupconsisting of aluminum, carbon, copper, stainless steel, nickel, zinc,silver, and combinations thereof.
 42. The method of claim 21, whereinthe solvent is selected from the group consisting ofN,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP),tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), tetramethylsilane(TMS), and dimethylformamide (DMF).